Method for killing organicsms in the course of conveying ballast water in ships and apparatus thereof

ABSTRACT

The present invention relates to gaseous discharge and applied biotechnology. In particularly, the present invention relates to a method for killing organisms in the course of conveying ballast water in ship, comprising applying a voltage with frequency of 400-40000 Hz between the anode electrode and the cathode electrode of the free radical generator, thereby forming strong ionization discharge of electric field strength of 250-600 Td between the anode electrode and the cathode electrode, ionizing, dissociating, and exciting O 2  and H 2 O, or O 2 , processing into active particles comprising O 3 , OH + and HO 2 , dissolving excitately to obtain free radical solution mainly consisted of OH + , adding the free radical solution to conveying pipeline of ballast water, conveying for 2-20 s in the pipeline, thereby obtaining killing organisms of ballast water selected from the group consisted of bacteria, single cell alga, and protozoan. It is capable to kill harmful invading microorganisms in the course of transporting ballast water without leaving any residual chemical reagent. The bacteria, single cell alga, protozoan, spore and vibrio, are eliminated and decomposed into H 2 O, O 2 , and small inorganic salt. It has no pollution and discharge, therefore, it can solve the problem of environmental pollution. The apparatus of carrying out above method comprises medium-high frequency electric source, ejector, gas liquid dissolution separator, liquid-liquid mixer, residual free radical treater, wherein a free radical generator is installed between the said ejector and the input raw material gas. The present method is capable of improving the quality of ballast water and is simple in operation and inexpensive.

FIELD OF THE INVENTION

[0001] The present invention relates to gaseous discharge and applied biotechnology, in particularly, the method for killing organisms in the course of conveying ballast water in ships and apparatus thereof.

BACKGROUND OF THE INVENTION

[0002] In 70^(th) decade last century, North American comb jelly invaded Caspian Sea and they eat plankton, fish berry and fry and brought a big calamity to anchovy and herring breeding. In 1990, a k nd of American organism of mnemiopsis invaded Caspian Sea and swallowed a large amount of plankton causing nearly exhaustion of fish fry in Caspian Sea. In 1997, AQIS estimated that over 170 kinds of marine organisms invaded Australian water area. Dinoflagellate barely has caused a loss of 80 million USD. They entered the human foodstuff chain via mollusks and endangered the human health Causing a quite long time discontinuity of Australian fishery industry. In 1996, there were 130 kinds of organisms invaded the Great Lakes in the boarder region between U.S.A. and Canada. Up to the year of 2000, inflicted economic loss reached 5 billion USD. ElTor, Inaba also brought Asian ElTor, Inaba to Latin America via ballast water of the ship. Invasion of foreign organisms via ballast water of ships will definitely bring disastrous destruction to the environment in Chinese offshore area and threaten the basis of continual development in our country's highly developing regions.

[0003] At the moment, many researchers are exploring to find an effective novel method to counteract the invasion of harmful organisms from ballast water of ships in order to solve the problem of regional limitation and obstacle to trade. In 1990, fishery organization of international union and of Great Lakes proposed measures to decrease the invasive spread of organisms by replacing ballast water in international waters. This measure could effectively lower or hinder the invasion of foreign organisms but replacement of ballast water in deep sea could not effectively and completely remove all the species at each stage of organisms in water. In 2000, IMO Protection Committee on Environment of Sea proposed “method of replacement of ballast water in deep sea (depth of sea below 2000 meters, farther than 200 nautical miles from shore)”. The said method, however, had the drawbacks of high consumption of energy and need of too long time of operation. In 2000, Geoff Rigby et al carried out respectively the researches on heating the ballast water But the method although seemed to be of potential attraction yet had also drawback of long operating time, high energy consumption and in addition formation of thermal stress which would lower the safety of cruise. Many scientists used chlorine and sodium hypochlorite to treat the ballast water. In order to kill micro-organism and to ensure the chemicals homogeneously dispersed in the ballast water, excess amount of 100-500 mg/L of chlorine should be added which to was scores of times of the amount used in common water treatment and as a result corrosion of facilities of cabin coating, pumps, pipes and etc would be aggravated. Further more, chlorine would react with organic matters in the ballast water to form carcinogenic organic chloride and the storage of several tons of liquid chlorine in the vessel would induce safety problem of leakage and explosion. Due to the above mentioned reasons, the said method is not possible to be used in the treatment of ballast water. Early in 1998, Snethurst proposed to re-evaluate the feasibility of using chlorine in the treatment of ballast water. Many scientists also carried out a large amount of exploratory research works while MEPC and GloBallast were of the opinion that at the moment there was not yet any effective method for on-line treatment of ballast water. At present, available methods comprise: (1) water replaced during cruise; (2) replacement of ballast water is carried out on shore of destinative harbor. The former has the problem of safety and high consumption of energy while the latter has the problem of investment by the local government and maintenance and management of harbor facilities.

DISCLOSURE OF THE INVENTION

[0004] The objective of the present invention is to overcome the shortcomings of prior art and provide simply operating and inexpensive method and apparatus capable of improving the quality of ballast water, killing harmful invading micro-organisms in the course of conveying ballast water and without leaving any residual chemical reagent. The novel method is based on application of strong ionization discharge and is capable of processing H₂O and O₂ in the molecular level into highly concentrated active particles comprising-hydroxyl (OH), ozone (O₃), thus obtaining free radical solution mainly consisted of OH by gas-liquid dissolution. When the OH⁺solution is added into the main conveying pipe for ballast water, harmful invading micro-organisms are killed and on-line treatment of ballast water is realized.

[0005] The present invention provides a method for killing organisms in the course of conveying ballast water in ship, comprising

[0006] applying a voltage with frequency of 400-40000 Hz between the anode electrode and the cathode electrode of the free radical generator, thereby forming strong ionization discharge of electric field strength of 250-600 Td between the anode electrode and the cathode electrode,

[0007] ionizing, dissociating, and exciting O₂ and H₂O, or O₂, processing into active particles comprising O₃, OH⁻and HO₂−,

[0008] dissolving excitately to obtain free radical solution mainly consisted of OH⁺,

[0009] adding the free radical solution to conveying pipeline of ballast water, conveying for 2-20 s in the pipeline, thereby obtaining killing organisms of ballast water.

[0010] The organisms is selected from the group consisted of bacteria, single cell alga, and protozoan.

[0011] According to the present invention, the active particles comprising O₃, OH⁻and HO₂ ⁺is dissolved in excited water activated by ejector, arising chain reaction to obtain free radical solution mainly consisted of OH⁻. The free radical solution further comprises HO₂ ⁻, HO₃ ⁻, O_(3—), O_(3—) ⁻, O_(2—), and H₂O₂ ⁻.

[0012] According to the present invention, the frequency between the anode electrode and the cathode electrode of the free radical generator is preferably 4000-10000 Hz, more preferable 6000-8000 Hz.

[0013] According to the present invention, the ballast water is treated by the apparatus for killing organisms of ballast water disposed in ship. The ¼ to {fraction (1/20)} of ballast water is taken out from main pipeline for conveying ballast water, dissolved excitately to obtain free radical solution mainly consisted of OH⁺, and returned to the pipeline. The time for killing organisms in the course of conveying ballast water is preferably 2 s-10 s.

[0014] According to the present invention, the free radical solution is formed by ejector, vortex impeller pump, and dissolution.

[0015] The present invention also provides a apparatus of carrying out the method for killing organisms in the course of conveying ballast water in ship, comprising medium-high frequency electric source, ejector, gas liquid dissolution separator, liquid-liquid mixer, residual free radical treater, wherein a free radical generator is installed between the said ejector and the input raw material gas.

[0016] The free radical generator is composed of anode electrode, cathode electrode, dielectric substance layer and septum.

[0017] According to the present invention, a layer of dielectric substance is disposed on the surface of the anode electrode, the surface of the cathode electrode, or the interstitial of discharge. The materials of the dielectric substance layer are porcelain, glass or enamel. The anode electrode, cathode electrode and dielectric substance layer are in the form of tube or plate.

[0018] The specific process of the present invention is as follows:

[0019] 1. Reaction Process for Obtaining Free Radical Plasma.

[0020] The production of hydroxyl free radical is described as an example.

[0021] In the case of weak ionization or relatively low electronic energy, OH is produced by the following reaction, i.e. high-energy electron directly dissociates and adsorbs water, and thus produces hydroxyl radical:

H₂O+e→H⁻+OH

H₂O+e→H+OH+e

[0022] The reaction processes for O₂ molecular ionization, dissociation ionization and charge exchange are as follows:

O₂ +e→2e+O₂ ⁺

O₂ +e→O⁻+O(³P, ¹D)

[0023] The reaction process for direct reaction between high energy state active particles and water to produce hydroxyl radical is as follows:

H₂O+O(¹D)→2OH

[0024] Under the action of strong electric field, the main route of forming hydroxyl radical is that O₂ ⁺ ion reacts with H₂O to form ionic group of water and then reacts with water again to form hydroxyl radical. The reaction processes are as follows:

O₂ ⁺+H₂O+M→O₂ ⁺(H₂O)+M

O₂ ⁺(H₂O)+H₂O→H₃O⁺+O₂+OH

O₂ ⁺(H₂O)+H₂O→H₃O⁺(OH)+O₂

H₃O⁺(H₂O)+H₂O→H₃O⁺+H₂O+OH

[0025] In the case of weak ionization discharge, every input of 100 eV energy could only ionization dissociate 0.3-0.4 molecule of H₂O, O₂, while in the case of strong ionization discharge, every input of 100 eV energy could ionization dissociate 2.07-1.23 molecule of H₂O, O₂, i.e. 2 O₂ ⁺takes place hydrated ion reaction to form OH radical. Therefore strong ionization discharge is the most effective method for formation of high concentration of hydroxyl radical.

[0026] 2. O₃ in Activated Water is Processed into Hydroxyl Radical Solution:

[0027] When quick running water flows through Venturi ejector or vortex impeller pump, it transiently cavitated into micro bubbles. When the diameter of the bubble is reduced to a specific dimension, the micro bubbles will rapidly expand, shrink to an explosion course. Just before the instant of bubble collapse, the temperature and pressure in the gas bubble rapidly increases (T>3000 k, P>1 kMPa). This makes the water molecule to stay in excited state. The concentration of free radical produced is about 10⁻⁹ (V/V). The amount of OH produced by excited water itself is quite small and it is a minor method for producing OH. The reaction involved is as follows:

H₂O→H⁻+OH

[0028] Chemical reaction between high concentration ozone and excited state water plasma is one of the main routes for producing high concentration of hydroxyl free radical and its proportionality concentration could reach 10 mg/L or more. The reaction involved is as follows:

O₃+3H₂O^(=31 →)3H₂O₂ ⁺

H₂O₂ ⁺→2OH⁻

O₃→O^(++O) ₂

O⁻+H₂O→2OH

O₃+H₂O→O₂+H₂O₂

H₂O₂—→H⁺+HO₂ ⁻

H₂O₂—+H₂O⁺→HO₂ ⁻+H₃O⁺

O₃+HO₂ ⁻→HO₂ ⁺+O₃ ^(—) ⁻

HO₂ ^(—)⇄H⁺+O₂ ^(—) ⁻

HO₂ ⁻+O₃→O₂+O₂ ^(—) ⁻+OH⁺

O₂ ^(—) ⁻+O₃→O₂+O₃ ⁻

H₂O₂+O₂ ^(—) ⁻→O₂+OH⁻+OH⁺

O₃ ^(—)+H⁺→HO₃+

HO₃ ⁺→O₂+OH⁺

O₂ ^(—)+HO₃ ^(+→2)O₂+OH⁻

[0029] The above-mentioned plasma reaction process indicates that the method of high concentration of ozone together with OH⁻dissolved in excited state water by strong process method is in engineering significance an effective method for processing hydroxyl radical.

[0030] 3. Method for Dissolution or Free Radical:

[0031] The dissolution of free radical meets Henry's law. The rate of dissolution of free radical can be expressed by the following equation: $C_{L}^{*} = {\frac{1}{H_{\Lambda}}C_{G}}$

[0032] Where C_(L) is the equilibrium concentration of free radical solution, indicating maximum free radical concentration dissolved in water at equilibrium state (also known as saturated concentration) and is correlated to parameters such as temperature of solution, partial pressure P of solute free radical in gas phase (gas phase free radical concentration), volume ratio of gas and liquid and the like.

υ=k _(L) ·a·(C ⁺ _(L) −C _(L))−k _(d) C _(L)

[0033] Therefore it is possible to raise the dissolution speed and to enhance the effective dissolution of free radical in water by increasing the liquid phase mass transfer rate of free radical k_(L)·a, expanding the gas liquid contact area, raising the free radical concentration in gas phase.

[0034] 4. Biochemical Process Involved in Killing Foreign Invading Microorganisms by Hydroxyl Radical:

[0035] The main processes involved in killing microorganisms by hydroxyl radical comprise peroxidation of lipid of living body, oxidative decomposition of amino acids, change of configuration of protein, cleavage of DNA chain and decoloration of cell colorant.

[0036] (1) Peroxidation of lipid; Under the action of hydroxyl radical, a series of reactions occur such as cleavage of lipid bond, chain cleavage of unsaturated fatty acid and hydrolysis. Finally decarboxylation of carboxylic acid decomposed from glycerophosphatide will yield CO₂ and H₂O.

[0037] (2) Oxidative decomposition of amino acids: Hydroxyl radical can decompose amino acid in the following way:

[0038] (3) Configuration change of protein: Hydroxyl radical can oxidize, cleave the disulfide bond and change the stereo configuration of protein, result in protein denaturation or deactivation of enzyme, and thus kill the invading organism.

[0039] (4) DNA chain cleavage: Hydroxyl radical reacts with DNA to form DNA adducts, which result in initial injury of DNA, followed by displacement or loss of DNA base and chain cleavage. In addition, base, sugar and phosphoric acid in DNA chain is attacked by hydroxyl radical to inflict chemical injury, which influence the structure and function of DNA and result in the death of cell.

[0040] (5) Decoloration of cell pigment: The hydroxyl radical can decolorate the pigment of photosynthetic microorganism or other photosynthetic microorganism, hinder their assimilation synthesis and thus kill the invading organisms.

[0041] The Beneficial Effects of the Present Invention Comprise the Following:

[0042] 1. It is feasible to kill the single cell alga, protozoan, spore, bacteria, vibrio and the like in the ballast water by hydroxyl radical at low concentration (0.6-0.7 mg/L).

[0043] 2. Time required for killing microorganism is extremely short (approximately 2.8 s). The killing of the harmful invading microorganisms can be done in the course of conveying ballast waster.

[0044] 3. The raw materials for processing hydroxyl radical are only oxygen and water. Nearly no cost of raw materials is needed.

[0045] 4 . The residual hydroxyl radical decomposes into H₂O and O₂ and no any residue is left.

[0046] 5. The quality of the ballast water is improved.

[0047] 6. The dimension of the apparatus for processing hydroxyl radical is small. The operation of the apparatus is simple and the cost of running the apparatus is low.

[0048] 7. By using the method of strong ionization discharge, it directly convert air, oxygen and water (or sea water) into hydroxyl radical solution. The bacteria, single cell alga, protozoan, spore and vibrio, are eliminated and decomposed into H₂O, O₂, and small inorganic salt. It has no pollution and discharge, therefore, it can solve the problem of environmental pollution.

DESCRIPTION OF THE FIGURES

[0049] The present will be further described with reference to Figures and Examples.

[0050]FIG. 1 is a schematic diagram for the structure of apparatus for producing hydroxyl radical and hydroxyl radical solution of the present invention.

[0051]FIG. 2 is a schematic flow diagram for the elimination of organisms in the course of conveying ballast water in ship of the present invention.

[0052]FIG. 3 is a schematic diagram of the structure of free radical generator.

[0053]FIG. 4 shows the relationship between the time needed to kill the microorganism by hydroxyl radical against the lethality rate.

[0054] In FIG. 1, the numbers indicate the following parts respectively: 1. pump, 2. flow meter, 3. free radical generator, 4. measuring apparatus for free radical concentration, 5. transformer, 6. inverter, 7. controller, 8.pump, 9. ejector, 10. separator of gas-liquid dissolution, 11. electrically operated valve, 12. back pressure valve, 13. treater for residual free radical, 14. concentration analyzer for hydroxyl radical.

[0055] In FIG. 2, the numbers indicate the following parts respectively: 15. unit for generating hydroxyl radical solution, 16. filter, 17. flow meter, 18. valve, 19. pump, 20. liquid-liquid mixer.

[0056] In FIG. 3, the numbers indicate the following parts respectively: 21. cathode electrode, 22. anode electrode plate (anode electrode+dielectric layer), 23. septum, 24. dielectric substance layer.

EXAMPLES

[0057] Free radical generator of the present invention was made of anode electrode 22, cathode electrode 21, dielectric substance layer 24 and septum 23. Strong electric field of 250-600 Td was formed between the anode electrode and cathode electrode. As showed in FIG. 1, after O₂ and H₂O, or O₂ molecules passed through valve 1 and flow meter 2, they were processed into OH⁺, O₃, HO₂ ⁺free radicals in free radical generator 3, which were controlled by electrically operated valve 11 and back pressure valve 12 and were processed with untreated ballast water suctioned by pump 8 into hydroxyl free radical solution in ejector 9 and gas dissolution separator 10. The undissolved free radicals were removed by residual free radical treater 13. High frequency electric source made from transformer 5, invertor 6 and controller 7 was used to supply electric source to free radical generator 3. Free radical concentration measuring apparatus 4 was used to measure the concentration of free radical produced while the hydroxyl radical solution concentration analyzer 14 was used to measure the concentration of hydroxyl radical solution. Untreated ballast water was suctioned by pump 19 into conveying pipe and filtered by filter 16 (FIG. 2). A part of them was taken out and was processed by free radical generating unit 15 into hydroxyl radical solution which was then mixed in liquid-liquid mixer 20 with ballast water conveyed in pipe and flowed through flow meter 17 and valve 18. The effectiveness of the elimination of single cell alga, protozoans and bacteria was illustrated in Table 1. TABLE 1 Results of the Test of Elimination of Bacteria and Protozoan Seawater OH Microorganism concentration concentration Lethality Species (mg/L) (count/mL) (%) Bacteria 0 1.9 × 10⁵ 0.63 not detectable 100 single cell 0 6.0 × 10⁴ alga 0.63 not detectable 100 Protozoan 0 4.4 × 10⁴ 0.63 not detectable 100

[0058] The time necessary for elimination of single cell alga, protozoan, bacteria and the like was extremely short. From the curve of relationship between time needed for elimination of microorganism by hydroxyl radical against the lethality in FIG. 4, time needed was about 4 s. Some experiment indicated that the time needed for 100% elimination of bacteria, single cell alga, protozoan, spore and vibrio was 2.8 s. Killing of organisms in the ballast water in the course of transporting ballast water in ship can be realized, so that gigantic facilities such as oxidation tower (contact tower) and aeration tank can be omitted.

[0059] The residual hydroxyl radicals were decomposed after 20 min into H₂O, O₂ and the like and there was no any residual chemical reagent left. At the same time, the present method can improve the quality of the ballast water as indicated in Table 2. Therefore the method for treating ballast water by using hydroxyl radicals solution is a green effective method. TABLE 2 Influence of OH on quality of ballast water ratio of OH solution (mg/L) change Item 0 0.63 (%) Nitrate 156.8 μg/ 184.1 μg/L +17.4 Nitrite 66.6 μg/L 1.1 μg/L −98.4 Ammonium 79.8 μg/L 0.4 μg/L −99.5 salt Phosphate 25.9 μg/L 32.9 μg/L +27.0 As 0.44 μg/L 0.43 μg/L −2.3 Cu 4.2 μg/L 2.6 μg/L −38.1 Zn 17.2 μg/L 68.6 μg/L +298.8 Cd 0.8 μg/L 0.7 μg/L −12.5 Pb 6.5 μg/L 1.6 μg/L −75.4 Fe 14.4 μg/L 8.6 μg/L −40.3 Hg 0.033 μg/L 0.031 μg/L −6.1 TOC 1.68 mg/L 2.39 mg/L +42.3 COD 0.54 mg/L Not detectable −100 DO 7.47 mg/L 13.24 mg/L +77.2 Salinity 31.351 31.349 0 pH 8.13 8.12 −0.1 Turbidity 0.4 0.2 −50.0 Electric 47.3 47.58 +0.6 conductivity 

what is claimed is:
 1. A method for killing organisms in the course of conveying ballast water in ship, comprising applying a voltage with frequency of 400-40000 Hz between the anode electrode and the cathode electrode of the free radical generator, thereby forming strong ionization discharge of electric field strength of 250-600 Td between the anode electrode and the cathode electrode, ionizing, dissociating, and exciting O₂ and H₂O, or O₂, processing into active particles comprising O₃, OH⁺and HO₂ ⁺, dissolving excitately to obtain free radical solution mainly consisted of OH⁺, adding the free radical solution to conveying pipeline of ballast water, conveying for 2-20 s in the pipeline, thereby obtaining killing organisms of ballast water.
 2. The method according to claim 1, wherein the organisms is selected from the group consisted of bacteria, single cell alga, and protozoan.
 3. The method according to claim 1, wherein the active particles comprising O₃, OH⁺and HO₂ ⁺is dissolved in excited water activated by ejector, arising chain reaction to obtain free radical solution mainly consisted of OH⁺.
 4. The method according to claim 1, wherein the free radical solution further comprises HO₂ ⁺, HO₃ ⁺, O₃ ^(+—), O₃ ^(+—), O₂ ^(+—), and H₂O₂ ^(.)
 5. The method according to claim 1, wherein the frequency between the anode electrode and the cathode electrode of the free radical generator is 4000-10000 Hz.
 6. The method according to claim 1, wherein the ballast water is treated by the apparatus for killing organisms of ballast water disposed in ship.
 7. The method according to claim 1, wherein the ¼ to {fraction (1/20)} of ballast water is taken out from main pipeline for conveying ballast water, dissolved excitately to obtain free radical solution mainly consisted of OH⁺, and returned to the pipeline.
 8. The method according to claim 1, wherein the time for killing organisms in the course of conveying ballast water is 2 s-10 s.
 9. The method according to claim 1, wherein the free radical solution is formed by ejector, vortex impeller pump, and dissolution.
 10. A apparatus of carrying out the method for killing organisms in the course of conveying ballast water in ship, comprising medium-high frequency electric source, ejector, gas liquid dissolution separator, liquid-liquid mixer, residual free radical treater, wherein a free radical generator is installed between the said ejector and the input raw material gas.
 11. The apparatus according to claim 10, wherein the said free radical generator is composed of anode electrode, cathode electrode, dielectric substance layer and septum.
 12. The apparatus according to claim 10, wherein a layer of dielectric substance is disposed on the surface of the anode electrode, the surface of the cathode electrode, or the interstitial of discharge.
 13. The apparatus according to claim 11 or 12, wherein the materials of the dielectric substance layer are porcelain, glass or enamel.
 14. The apparatus according to claim 13, wherein the anode electrode, cathode electrode and dielectric substance layer are in the form of tube or plate. 